Condensation products of n,n&#39;-bis (alkoxymethyl) urea and processes for their production



Patented May 1, 1945 CONDENSATION PRODUCTS N,N'-BIS (ALKOXYMETHYL) UREAAND PROCESSES FOR THEIR PRODUCTION v William J. Burke, Marshallton, andJames H. Werntz, Wilmington, Del., assignors to E. I. du Pont de Nemours& Company, Wilmington, DeL, a corporation of Delaware No Drawing.Application November 21, 1942, Serial No. 466,472

6 Claims.

This invention relates to new condensation products and moreparticularly refers to new derivatives of diamides having a variety ofuses in the industrial arts and processes for their production.

There occur in nature certain materials which display surface-tensionmodifying properties and which have been used to a limited extent asemulsifying agents and protective colloids. Such products are relativelycostly, diflicult to isolate ture with the numerous surface-activeagents of the prior art. A still further object is to produce a newclass of surface-active agents in pure form, and unsuitable for many ofthe applications of modern industry which employ surface-tensionmodifying agents. Solubility in water of this non-ionic type of agent,however, does not depend on anionic or cationic solubilizing groups andit is therefore substantially unaffected by the presence of salts suchas may be present in hard water and of acids and bases, for example, theones customarily employed in textile-treating operations. Recognizingthat a synthetic product of this type will enjoy a wider field ofusefulness than the naturally occurring materials, earlier investigatorshave sought to prepare emulsifying agents by modifying certainpolyethers and certain polyhydroxy compounds which are obtainable fromsugars by the introduction of suitable organic radicals. Theseinvestigations served to confirm the utility of the non-ionic type ofsurface-tension modifying agent and to emphasize its superiority tosoap, especially in hard water. However, the commercial scope of theseprior developments has been limited .by .the high cost and relativescarcity of suitable intermediates. Furthermore, the development andcommercial util zation of synthetic non-ionic detergents'and emulsifyingagents has been seriously hampered by the lack of practical methods. ofmanufacture which have been limited both in scope and in yieldperformance. Hence, the discovery of a novel and practical synthesis ofnon-ionic surface-tension modifying agents from low-cost readilyavailable raw materials according to the process of this inventioncomprises an important and valuable advance in the field ofsurface-active chemistry.

It is an object of this invention to produce new non-ionicsurface-tension modifying prodface-active agents which maybe used alone,in admixture with one another, and/or in admixwhisch are free from manydisadvantages of prior art agents of this type. A still further objectis to produce a new class of condensation polymers by means of a simpleand expeditious process employing a variety of reactants which arerelatively cheap and readily available. Additional objects will becomeapparent from a, consideration of the, following description and claims.

These objects are attained in accordance with the present inventionwherein an N,N'-bis(alkoxymethyl) derivative of a diamide is reactedwith an organic compound substituted with two or more hydroxyl groupsand said reaction is carried out in the presence of a, third organiccompound containing at-least eight carbon atoms and at least onehydrogen atom which iss'directly attached to oxygen,'nitrogen 0r sulfur.In a more restricted sense this invention is concerned with a processwhich comprises reacting an N,N'--bis'(alkoxymethyl) derivative of adiamide containing less than seven carbon atoms with a monomericpolyhydric alcohol and the third component referred to in the precedingsentence. In a still more restricted sense this invention is concernedwith the reaction of N,N-

bis(alkoxymethy) -urea with a glycol and a monofunctional organiccompound having from eight to eighteen carbon atoms and further having ahydrogen atom which is attached to oxygen, nitrogen or sulfur. In apreferred embodiment, this invention is directedto the reaction ofbis(methoxymethyl)urea, with a glycol and amonosulfonamide derived frompetroleum hydrocarbons of at least eight carbon atoms.

In another preferred embodiment the invention is concerned with thereaction of bis(methoxymethyl) urea with diethylene glycol and analiphatic monohydric alcohol of from eight to eighteen carbon atoms.Additionalembodiments of the invention comprise carrying out theforegoing reactions under carefully controlled is included in thereaction mixture a N,N'-bis(alkoxymethyl) derivatives of diamides of thestructure ROCH2NIiR'-NHCH2OR1I1 which R is the nonhydroxy portion of amonohydric alcohol boiling below 210 at 760 man. and the bivalentradical R is the residue of a diamide such as urea. By including in thereaction mixture an organic compound which contains at least onefunctional group and is capable of reacting with these N,N' alkoxymethylcompounds, modified condensation polymers are obtained. When themodifying organic compound contains 8 or more carbon atoms and is usedin suitable proportions new water-soluble products are obtained whichpossess useful surface-active properties.

Certain probable reactions have been postulated to explain the formationof a product obtained by this invention. By way of illustration only andimposing no limitation whatsoever. the following reactions arepresented, recognizing that no structural data are available and thatthe products are probably of greater complexity than indicated.Bis(methoxy-methyl)urea probably reacts with an equimolecular quantityof ethylene glycol as follows: xcmoomNnooNr'icmocHa+xH0cH,oHg0H-CHaO(CHzNHCONHCHzOCHzCH:O)=H+2X-l onion Now if one mole of dodecanol-lfor each 5 moles of bis(methoxymethyl)urea and ethylene glycol probablereaction mechanism is as follows: C H H+5CHaOCH:NHCONHCHi0CHs+'OCHICHQOH 011E350(CHgNHCONHCHzOCH2CH2O 5H+10CH|OH 0n the other hand, twomoles of dodecanol-l, '9

moles ethylene glycol and moles bis(methoxymethyl) urea may react asfollows:

ally employed are equimolecular amounts of the N,N'-bis(alkoxymethyl)compounds and a glycol plus 0.5-0.025 mole of an organic compound of 8or more carbon atoms having at least one labile hydrogen atom.

The products of this invention range from oils and soft resins to fattyor wax-like solids. Their solubility characteristics depend upon thekind and length of the polymer chain formed and upon the nature of themodifying organic compound. The solutions and emulsions, respectively,are stable to weak acids and alkalis and the agents causing hardness inwater. The preferred products are, generally speaking, soluble orreadily dispersible in water and in organic solvents. such as ethylalcohol, acetone, benzene, ethylene I dichloride, textile finishingoils, ethyl ether, pe-

troleumether, white mineral oil, castor oil, etc. The invention may bemore readily understood by a consideration of thefollowing illustrativeexamples, wherein the quantities are stated in parts by weight.

' EXAMPLEI Bis(methoa:ymethyl) urea-diethanolamiae polymer modified withdodecanol-I Seventy-four parts bis(methoxymethyl)urea,

I CuHuOCHrNHC ONHCH:(O CHgCHzO CHLINHC ONHCHIMO CnHgg-L-ZJCH OHRegardless of the actual proportions employed, the products probablyconsistof each of the indicatedtypes. Many of the products of thisinvention may be described as condensation polymers of 40- X moles of amonomeric polyhydric alcohol, 40 moles of a N,N-bis(alkoxymethyl)derlvative of a diamide and 1-20 moles of an organic compound of 8 ormore carbon atoms having a labile hydrogen atom in which X is a wholenumber ranging from 0' to 20.

In accordance with this invention, the general procedure for preparingthese new non-ionic surface-active polymers is to heat the reactant withor without a catalyst under conditions such that the low molecularweight alcohol which is formed can be removed from the reaction mixture.The conditions used vary considerably with the type of modifyingcompound used and the monomer being polymerized. Glycols react readilyin the absence of a catalyst. However, it is frequently desirable toaccelerate the rate of reaction or to carry out the reaction at a lowertemperature and the condensation is then conducted in the presence of asmall amount of an acid or acidic salt as catalyst and under suchconditions that-the alcohol formed will be removed from the sphere ofreaction as rapidly as possible. 'I'his is conveniently done by carryingout the reaction in the presence of a catalyst at a temperature abovethe boiling point of the low molecular weight alcohol, such asmethanoL'and with nitrogen or other inert gas bubbling through thereaction mixture to carry off the alcohol as rapidly as. it is formed.The preferred proportions usuanol-l one may use octanol-l,hexadecanol-l, oc- 'tadecanol-l, octadecene-9,l0-ol-1, pentadecanol- 8,heptadecanol-9 or the related tertiary alcohols. Technical mixtures ofalcohols obtainable by the carboxylic reduction of coconut oil, spermoil, lard oil, beef tallow, castor oil, peanut'oil, drying oils, etc.may be employed. The higher alcohols obtainable as by-products in thesyn-" thesis of methanol by also be used.

EXAMPLE II catalytic processes may Bis(methoa:ymethyl) urea-diethyleneglycol poly-l met modified with a. white oil sulfonamide was a brown,elastic, chicle-like polymer. It dis solved in water to-give slightlycloudy, sudsing solutions.

Ten part of the above condensation product and. 1 part of ammoniumchloride were dissolved in 200 parts of water and the solution appliedby padding to a piece of gabardine cloth. The

' treated fabric was dried by heating at C. in

a forced draft oven for 3 minutes. This treatment served to insolubilizethe finishing agent since the treated fabric was now water repellent.

The white oil sulfonamide was obtained by treating with ammonia thesulfonyl chloride prepared from white 011 by the process described inReissue Patent No. 20,968. White oil is a petroleum fraction, boilingwithin a certain range, which has been refined by an acid washingtreatment. The product referred to herein is the same as that describedin U. S. Patent No. 2,197,- 800 at page 3, column 2, lines 49-68, whereit is minutes the product was a viscous resin, soluble stated that, thedistillation range specified will cover only those straight chain ornormal hydrocarbons of about 13-20 carbon atoms. The white oilsulfonamide analyzed 4.7% nitrogen, 9.7% sulfur, 2.1% chlorine and hadan estimated molecular weight of 291.

The above condensation product in which the rated aliphatic hydrocarbonssuch as kerosene fractions, paraffin wax, alicyclic hydrocarbons, etc.

Sulfonamides derived from thiols can also be employed. For example, themixture of alcohols obtainable by the carboxylic reduction of coconutoil was converted to a mixture of alkyl chlorides, then to a mixture ofalkyl thiols, then to a mixture of alkyl sulfonyl chlorides, and finallyto a mixture of alkyl sulfonamides. Ten parts oi this mixture ofsulfonamides, 29.6 parts bis(methoxymethyl) urea, 21.2 parts diethyleneglycol were stirred together while blowing with nitrogen gas. Afterheating on the steam bath about 2 hours about 13.0 parts of volatileby-products had been removed. The condensation product gave stronglysudsing solutions in water. Sulfonamides may also be employed which maybe derived from the thiols and mixtures of thiols which contain thehydrocarbon radicals disclosed for the alcohols in Example I.

Exnrru: III

Bis methoxymethyl urea-diethylene glycol polymer modified withdodecanol-I One mol bis(methoxymethyl)urea, 0.9 mol in water to yieldsudsing solutions.

In place or the long-chain thioethers derived from thiosorbitol one mayemploy the long-chain monoand diethers of glycerin such as monododecylglyceryl ether. One may also-use monolaurin, monostearin and technicalmixtures of monoglycerides obtained from sperm oil, bee! tallow, castoroil, peanut oil, drying oils etc.

Exauru: V

Bis(methorflmethyl)ureu-diethylene glycol polymer modified withhexadecane-I-thiol One mol bis(methoxymethyl) urea, 0.9 mol diethyleneglycol, 0.2 mol hexadecane-l-thiol were heated at 120-130 C. whileagitating with ..a

diethylene glycol, 0.2 mol dodecanol-l were heated together at 120-130C. while agitating with a stream of nitrogen gas. After heating about 30minutes the condensation product was a soft. clear, viscous resin. Itdissolved readily in cold water to yield sudsing solutiona.

A product with similar properties was obtained by heating on the steambath for one hour a mixture of 1 mol bis(methoxymethyl) urea, 1 moldiethylene glycol and 0.1 mol dodecanol-l.

In place of dodecanol-l one may use other alcohols, examples of whichare disclosed in Example I. In place of alcohols one may also use acids,examples of which are caproic acid, palmitic acid, stearic acid, oleicacid, diheptylacetic acid.

etc. Technical mixtures of acids occurring in coconut oil,- sperm oil,beef tallow, castor oil, peanut oil, drying oils, etc. may also beemployed. The higher acids obtainable by the oxidation of petroleumhydrocarbons and waxes may also be used.

EXAMPLE IV Bis(methoxymethyllure -diethylene glycol polymer modifiedwith 1dodec'ylthiosorbitol one mol bis(methoxymethyl)'urea, 0.9 moldiethylene glycol. and 0.2 mol l-dodecylthiosorbitol were heated at120-130 C. w hile agitating witha stream oi nitrogen gas. After heating20 stream of nitrogen gas. After heating 30 minutes the product was asoft, viscous resin. It was soluble in water to yield strongly sudsingsolution.

In place of hexadecane-l-thiol, one may employ the thiols or mixtures ofthiols which contain the hydrocarbon radicals disclosed for the alcoholsin Example I.

' EXAMPLE VI Bls(metho:cymethyl) urea-diethylene glycol polymer modifiedwith stearamide One mol stearamide. 5 mols diethylene glycol, 5 molsbis(methoxymethyl)urea were heated on the steam bath while agitatingwith a stream of nitrogen gas. After heating 3.5 hours the product was asoift, white solid. It gave sudsing dispersions in water.

Similar product was obtained in 30 minutes when a small amount 01ammonium chloride was included in the reaction mixture. This product wasnot quite as soluble in water as the above condensation product in whichno catalyst was employed.

In place of stearamide one may employ lauric amide, caprylic amide,palmitic amide, the amide oi diheptylacetlcacid, etc. Technical mixturesof amides obtainable from the mixtures of acids occurring in coconutoil, sperm oil, beef tallow, castor oil, peanut oil, drying oils, etc.may also be used. The amides of the higher acids obtainable by theoxidation of petroleum hydrocarbons and waxes may also be employed.Ureides and monosubstituted amides such as N-methyl lauramide may beused.

In place of amides one may also use amines such as N-dodecylamine,N-octylamine, N-hexae d ng agents decylamine, N-octadecylamina'N-oleylamine, pentadecyl-a-amincor related secondary amines such asN-octyl-N-methylamine, dioctylamine,

etc. Technical mixtures of amines derived from the mixture of acidsoccurring in coconut oil, sperm oil, beef tallow, castor oil, peanutoil, drying oils, etcamay also be employed. Catalysts are usuallyrequired when amines are employed as Emmett VII I Bls methoxymethyburea-diethylene ulvcol polymer modified with methylol stearamide Fivemols methylol steal-amide, 25 mols diethylene glycol and 25 mols ofbls(methoxymethyl) urea were heated at 120-130 C. for 30 minutes andthen at 100 C. for 30 minutes; .The product was a soft, white solidwhich gave sudsing dis-,

persions in water.

In place or methylol stearamideone may cmploy the methylolamldes formedby reaction of formaldehyde with the amides disclosed in Example VI.

ROCHzNHR'NHCHaOR in which R is the nonhydroxy portion of a monostabilityand basicity of the polymer ingredients.

hydric alcohol boiling below 210 C. at 760 mm.

and is preferably a hydrocarbon radical. Th 2.1- cohols'corresponding tothe radicals R include methyl, ethyl, propy isopropyl, butyl, isobutyl;

amyl, hexyl, octyl, benzyl, furfuryl, tetrahydrofurfuryl, methoxyethyl,ethoxyethyl alcohols, and in general any monohydric alcohol boilingbelow 210 C. at 760 mm. For the purposes of this invention thesealcohols should advisably be more volatile than the modifying organiccompound and in general methyl alcohol is preferred since it is readilyremoved. The bivalent radical R is the residue of a diamide and.preferably of 8 or less carbon atoms since with highercontentdecyldimethyl of carbon the condensation products have too lowsolubility in water. fe'rred diamide, thiourea amides of the followingdibasic acids may also be employed: Adipic, succinic, maleic, malonic;oxalic, phthalic, etc.

In general, glycols which R OH groups attached to different aliphaticcarbon atoms and not containing other reactive groups are preferred'foruse as polymer ingreclients. However, aromatic residues may form part ofa molecule provided the hydroxyl groups are While urea is the preof theformula non'on in attached, to aliphatic carbon atoms. Hetero-.

atoms such a oxygen, sulfur, NH and NR may also form part ,of thediradical, R as for example in the polyethylene glycols, indiethanolamine, and in diethanolethylamine. Since the reactivity of thehydroxyl groups is greatest if they are pri'-. mary and least if theyare tertiary, compounds having primary hydroxyl groups are to bepreferred to those having secondaryv groups and those having secondarygroups amples of suitable glycols include ethylene glycol, diethyleneglycol, 'triethylene glycol, hexamethylene" glycol, 1,3-butylene glycol,-etc. Higher polyols such. as glycerin,,erythritol, pentaerythri-- tol,sorbitol, l-thiosorbitol, glucose, alpha-methyl glucoslde can also beused but, as is to be expected, the products while useful are probablynot linear and their use may result in the formation of products '01 lowsolubility in water.

Organic compounds suitable for. modifyin -the polymer and containing atleast one labile hydrogen atom, i. e., hydrogen directly attached tooxygen, nitrogen or sulfur, and at least 8 carbon atoms include thealcohols, monoglycerides, alkyl phenols, for example, secondary dodecylphenol, amides, ureides,-. N-substituted ureas such as N- octylurea,N-substituted anilines such as N-dodecylaniline, sulfonamides, thiols,thioetherssuch as l-dodecylthiosorbitol, acids, methylolamides,

-monoalkyl glycerylethers, esters of hydroxyacetic acid, etc. In generalthe mono-functional compounds are preferred. .The monosulfonami'des arepreferred since they condense rapidly to yield products of:ood'solubiiity in water. 1

catalyst .used variesconsiderably with the may also be used. Di

is a divalent .radical having the two are to be preferred to thosehaving tertiary hydroxyl groups. Ex

. tion products without reaction is carried out In many cases nocatalyst is required. However, the use of acatalyst reduces materiallythe reaction time, and the reaction may be carried out successfully atslightly elevated temperatures. Basic ingredients require acidiccatalysts while some neutral monomers such as bis(methoxymethyDureawhich undergo troublesome crosslinking reactions at high temperatures inthe presence of strong acid catalysts can be condensed with glycolswithout the use of catalysts. Strong acids, materials easily convertedto strong acids, salts of strong acids and weak bases, andtrialkylsulfonium iodides and sulfates are catalysts for this reaction.These catalysts may be designated as acetal-forming oracetal-interchange catalysts. Specific catalysts include suifuric acid,hydrochloric acid, phosphoric acid, p-toluene sulfonic acid, dimethylsulfate, diethylmethyl sulfonium methylsulfate, methylphenyloctadecylsulfonium methylsulfate, iodine, almmonium chloride, zinc chloride,magnesium bromide, diethylmethyl sulfonium iodide and dosulfoniumiodide. It is frequently desirable to prepare the water solublecondensacatalysts Aqueous solutions or dispersions of these productsincluding a small amount of one of the above mentioned catalysts arethen employed to impregnate fibrous materials such as paper, cloth,wood, etc. The impregnated material is then heated at an elevatedtemperature to insolubilize the product and produce uniquewater-resistant finishes.

- The temperature at which the polymerization varies with the stabilityof the reactants involved. Since the rate of 0011-: densation increaseswith increasing temperature it is usually-advantageous .to use as high atemperature as is possible without decomposition or other unfavorableside reactions. In general the temperature lies between about 50 C. and250 C. with the optimum temperature between about 80 C. and 200 C. Inorder to prevent loss of volatile reactants and to avoid heating. atvery high temperatures the initial stages of the polymerization may becarried out at a relatively low temperature and the later stages at ahigher tem perature. The maximum temperature employed isdependent uponthe catalyst used since it has ly by heating the polymerization mixtureunder hot reactants to reduced pressure especially during the latterstages of the cycle. The same effect can also be obtained by passing aninert gas through the formed. The latter method is effective at atmospheric, subatmospheric or superatmospheric pressure. A similar method isto use an inert liquid such as toluene as the solvent. The solvent isrefluxed in a column and the. lower boiling alcohol removed from the topof the column by distillation. 1 1

Additional information concerning the conditions of reaction suitableforuse is set-forth in detail in the co-' pending application, SerialNumber 464,244, filed by the-present applicants on November 2, 1942, andentitled, Condensation products and proccarry off the alcohol as-it isand the individual reactants as textile esses for their production. Byusing the diamide derivatives previously described herein in place ofthe heteromonocyclic urea derivatives described in that application theinstructions thereof become applicable hereto.

The new compositions disclosed in this invention which have a modifyingradical of 8 or more carbon atoms belong to-the class of capillaryactivematerials in that they have colloidal properties and therefore may beadvantageously used in any process involving wetting, penetrating,deterging, dispersing, emulsifying, frothing, foaming, and kindredphenomenon. These compositions may be employed in pure or standardizedform and if desired in conjunction with known processing or treating.agents. They may be used by themselves or in combination with othersurface-active agents in any relation in which surface-active agentshaving colloidal properties have heretofore been used in the textile,leather, lacquer, paper, rubber and like industries. A few of the moreimportant uses of these new products assistants will bementioned inorder that the importance and widespread applicability of these newproducts in the textile industry may be fully appreciated. They may beused alone or in combination with suitable detergents for cleansing andscouring vegetable and animal fibers when removing fatty or oilymaterials or in general in place of soap for cleansing operations. Theymay advantageously be employed as cleansing agents in hard water. Theproducts have capillary active properties of different degree dependingupon the nature and the length of the water solubilizing polymer chainand the consequent degree of solubility and dispersing power in water.Furthermore, the nature and length of the modifying radical alsocontributes its influence on the degree of solubility and dispersingpower in water. These products areuseful as auxiliary agents for variouspurposes in the dyeing industry, for instance as dyeing agents, levelingassistants and the like. The new products may be used with agentspreventing the precipitation on the fiber of insoluble inorganic saltscaused by the hardness of the water. If desired they may be used inadmixture with adjuvants, for instance water soluble salts of phosphoricacids such as alkali pyrophosphates or alkali metaphosphates, otherinorganic salts for instance those used for altering the pH value of themixture such as sodium carbonate, sodium silicate, or pure diluents suchas sodium sulfate or sodium chloride, bleaching agents or the like.

As many widely diiferent embodiments of this invention may be madewithout departing from the spirit and scope thereof, it is to beunderstood that the invention is notlimited to the specific embodimentsthereof except as defined in the appended claims.-

We claim:

1. A process for preparing water-soluble condensation products whichcomprises reacting at C. to 250 C. an N,N'-bis (alkoxymethyl) urea witha glycol and a monosulfonamide of a straight chain hydrocarbon havingfrom about thirteen to about twenty carbon atoms.

2. A process for preparing water-soluble condensation products whichcomprises reacting at 50 C. to 250 C. bis(methoxymethyl) urea with aglycol and a monosulfonamide of a straight chain hydrocarbon having fromabout thirteen to about twenty carbon atoms.

3. A process for preparing a water-soluble condensation product whichcomprises reacting at about C. bis(methoxymethyl)urea with diethylene'glycol and a monosulfonamide of a straight chain hydrocarbon having fromabout thirteen to about twenty carbon atoms.

4. Products produced in accordance with the process defined in claim 1.

5. Products produced in accordance with the process defined in claim 2.

6. Products produced in accordance with the process defined in claim 3.

. WILLIAM J. BURKE. JAMES =1. waan'rz.

